Cationic derivatives of 4,4&#39; - bis-(s-triazinylamino)-stilbene -2,2&#39;-disulfonic acid,process for the preparation thereof and application as optical brighteners

ABSTRACT

CATIONIC COMPOUNDS OF THE 4,4&#39;&#39; - BIS (S - TRIAZINYLAMINO) - SILBENE - 2,2&#39;&#39; / DISULFONIC ACID SERIES ARE USEFUL AS OPTICAL BRIGHTENERS FOR FIBROUS MATERIALS, ESPECIALLY CELLULOSE MATERIALS. THESE BRIGHTENERS ARE COMPATIBLE WITH CATIONIC AUXILIARIES AND OPERATIVE WHEN WORKING AT LOW PH VALUES AND THUS CAPABLE OF APPLICATION TOGETHER WITH CATION-ACTIVE LAUNDRY REFINING AGENTS OR CREASE-RESISTANT FINISHING AGENTS. THEY ARE, FURTHERMORE, USEFUL FOR BRIGHTENING PAPER PULPS OR PAPER COATINGS.

United states Patent 01 iice 3,663,538 Patented May 16, 1972 US. Cl. 260--240 B Claims ABSTRACT OF THE DISCLOSURE Cationic compounds of the 4,4 bis (s triazinylamino) stilbene 2,2 disulfonic acid series are useful as optical brighteners for fibrous materials, especially cellulose materials. These brighteners are compatible with cationic auxiliaries and operative when Working at low pH values and thus capable of application together with cation-active laundry refining agents or crease-resistant finishing agents. They are, furthermore, useful for brightening paper pulps or paper coatings.

Derivatives of 4,4 bis (s triazinylamino) stilbene- 2,2-disulfonic acid are already known in great number. As optical brighteners they have an outstanding economical importance. Of the water-soluble derivatives of this category of compounds only such products have been described hitherto in which the active brightener molecule is present as an anion (Type A):

In this formula, Y and Z represent neutral or negatively charged substituents, and M represents a cation. It may be assumed that the soluble alkali metal salts and equally the salts of the 4,4 bis (s triazinylamino) stilbene- 2,2-disulfonic acid with amines dissociate in aqueous solution to a large extent into their ions, and that also the free disulfonic acids are dissociated, at least partially, into hydrogen ions and brightener anions, provided they are soluble in water. Also on the substrate ionic relation indicated in formula A is maintained. This is equally true for substrates such as cellulose fibers on which these brighteners are absorbed substantively, and for substrates with basic groups, such as polyamide and protein fibers on which the brightening anion is bound mainly in heteropolar manner on cationic centres.

From this type of anionic brighteners there may be distinguished such water-soluble derivatives of the 4,4- bis (s triazinylamino) stilbene 2,2 disulfonic acid in which the active brightener molecule is present as a In this formula, Y and Z represent electro-neutral bridge members and X represents an anion.

The present invention relates to compounds of the type B and to a process for their preparation, and it demonstrates the clear advantages on some fields of application of these cationic derivatives over the above-mentioned anionic brighteners.

Now, we have found that compounds of the general Formula I G NR A NgR wherein A and A which may be the same or represent hydrocarbon radicals containing 2 to 8 carbon atoms and which may be substituted by non chromophoric radicals, R and R which may be the same or dilferent represent hydrogen or lower alkyl groups containing 1 to 5 carbon atoms, R R R and R which may be the same or diiferent, represent lower alkyl groups containing 1 to 5 carbon atoms, a cycloalkyl group, preferably a cyclohexyl group, an aralkyl group, preferably a benzyl group, or an aryl group, preferably a phenyl group, and wherein each R and R as well as R and R may form, together with the nitrogen atom, a hydrogenated heterocyclic ring and R and R which may be the same or dilferent, represent hydrogen, a lower alkyl group containing 1 to 5 carbon atoms or a benzyl group, and X represents a colorless anion, can be prepared by a process wherein the condensation product obtained in known manner from 1 mol of 4,4 diamino stilbene 2,2 disulfonic acid and 2 mols of cyanuric acid chloride is reacted at temperatures of about 20 to 40 C. with 2 mols of a diamine of the general Formula 11 wherein A, R R and R have the meanings indicated above, the reaction product obtained is further condensed at temperatures of from about 40 to about 100 C., preferably at 40 to about C. with at least 2, preferably with 4 mols, of a diamine of the Formula III wherein A, R R and R have the meanings given above, the reaction product obtained is separated with 2 mols of the compound wherein R has the meaning given above and X represents a radical that may be split off as anion, in the form of an inner salt of the general Formula IV wherein R R R R R R R", A and A have the meanings given above, and the compounds of the Formula IV are reacted with at least 2 mols of a compound of the formula wherein R has the meaning given above and X represents a radical that may be split off as anion.

The sodium salt of the 4,4'-bis-(2,4"-dichloro-s-triazinylamino-(6") )-stilbene-2,2'-disulfonic acid obtained from 1 mol of 4,4'-diamino-stilbene-2,2-disulfonic acid and 2 mols of cyanuric acid chloride is combined, if the diarnines II and III are identical, with at least 4 mols, preferably with 6 mols, of this diamine. By heating to a temperature of about 40 C. for about 4 hours, in each of the two s-triazine rings first 1 chlorine atom and by subsequent heating to a temperature of about 100 C., preferably to about 80 C., the second chlorine atom is replaced by the radical of this diamine.

Working up may be effected as follows: the condensation products are first dissolved by addition of water and concentrated sodium hydroxide solution, the solution is clarified by addition of charcoal and the sodium salts of the Formula IVa its R 2 IVa wherein R R R R R R A and A have the meanings given above, are separated by addition of sodium chloride. From the strongly alkaline aqueous solution of the sodium salts the diliicultly soluble inner salts 1V (R"=hydrogen) can be separated by addition of acid up to a pH-value of 9 to 10. These salts can be easily identified by an analytic or titrimetric methods.

The inner salts IV wherein R represents a lower alkyl group can also be precipitated from the strongly alkalineaqueous or aqueous-alcoholic solution of the sodium salts IVa by addition of 2 equivalents of an alkylating agent such as, for example, dimethyl sulfate. These salts too mu be easily determined analytically.

Moreover, the following method of operation may be used: the aqueous solution of the sodium salts IVa is combined with such a quantity of acid that the internal salts of the Formula IV (R' zhydrogen) which have precipitated intermediately are dissolved again. In this case, clarification may be effected in an acid medium and the internal salt of the general Formula IV (R' -=hydrogen) can be precipitated again by addition of sodium carbonate up to a pH-value of 9 to 10.

As diamines of the Formulae II and III there may preferably be used:

N,N-diethyl-1,2-diaminoethane, N,N-di-n-propyl-1,2-diaminoethane, N,N-di-n-butyl-1,2-diaminoethane, N,N-di-n-pentyl-1,2-diaminoethane, N,N-diethyl-N'-methyl-l,Z-diaminoethane, N,N,N'-triethyll ,Z-diaminoethane, N,N-di-n-butyl-N'-ethyl-1,2-diaminoethane, 1-diethylamino-Z-amino-n-propane,

S Oa

N-methyl-N-ethyl-1,3-diamino-n-propane, N,N-diethyl-l ,S-diaminopropane, N-methyl-N-n-propyll,3-diamino-n-propane, N,N-di-n-propyll ,3-diamil10-n-propane, N-ethyl-N-n-butyll ,3-diamino-n-propane, N,N-di-n-butyll,3-diamino-n-propane, N,N-di-n-pentyl-1,3-diamino-n-propane, N,N-diethyl-N'-methyl-1,3-diamino-n-propane, N,N,N'-triethyl-1,3-diamino-n-propane, N,N-diethyl-N'-n-propyll,3-diamino-n-propane, N,N-diethyl-N'-n-butyll,3-diamino-n-propane, NgN-di-n-butyl N ethyl=1,3-diamino-n-propane, N-methyl-N-cyclohexyld ,3-diamino-n-propane, N-ethyl-N-benzyl-1,3-diamino-n-propane, N-ethyl-N-phenyll ,S-diamino-n-propane, 'y-piperidino-n-propylamine, 'y-morpholino-n-propylamine, N,N-diethyl-1,4-diamino-n-butane, N,N-di-n-propyl-l,4-diamino-n-butane, N,N-di-n-butyll ,4-diamino-n-butane, N,N-diethyl-N'-methyl-1,4-diamino-n-butane, N,N,N'-triethyl-1,4-diamino-n-butane, N,N-di-n-butyl-N-ethyl-1,4-diamino-n-butane; 1diethylamino-4-amino-n-pentane, l-di-n-butylamino-4-amino-cyclohexane, l-di-n-butylamino-4-amino-n-pentane, 1-diethylamino-4-methylamino-n-pentane, 1-diethylamino-4-ethylamino-n-pentane, 1-di-n-butylamino-4-ethylamino-n-pentane, 1-diethylaminoA-amino-cyclohexane, 1-di-n-propylamino-4-amino-cyclohexane, ldi-n-butylamino-4-amino-cyclohexane, 1-diethylamino-3-amino-cyclohexane, 1-di-n-propylamino-B-amino-cyclohexane, 1-di-n-butylamino-3-arnino-cyclohexane, l-diethylamino-2-amino-cyclohexane, l-di-n-propylamino-2-amino-cyclohexane, 1-d.i-n-butylamino-2amino-cyclohexane,

( 4-amino-benzyl) -diethylamine,

fl- (p-aminophenyl -ethyl-diethylamine,

B- (p-aminophenyl) -ethyl-di-n-propylamine, l-aminomethyl-4-dimethylaminomethyl-benzene, 1-aminomethyl-4-dimethylaminornethyl-cyclohexane; Z-amino-dimethylaniline, 3-amino-dimethylaniline, 4-amino-dimethylaniline, B-amino-diethylaniline,

4-amino-diethylaniline, 2-amino-4-dimethylamino-toluene, 4-amino-2-dimethylamino-toluene, 4-amino-2-diethylamino-toluene, 6-chloro3-amino-dimethylaniline, 2-chloro-4-amino-dimethylaniline, 6-bromo-3-aminodimethylaniline.

The three last-mentioned substances are starting products for the preparation of compounds of the Formula I, wherein A or A are substituted by non-chromophoric groups, i.e by halogen atoms. Other non-chromophoric groups that may be used are cyano groups, lower alkoxy groups and lower carboxylic acid-alkyl ester groups.

From the internal salts IV the compounds I of the present invention wherein R and R represent hydrogen are obtained by stirring the internal salts IV in water and dissolving them by addition of 2 equivalents of acid. It is advantageous, in order to obtain completely clear and stable solutions, to increase the amount of acid slightly and to adjust to a pH-value of about 5. [AS acids, strong inorganic acids, such as hydrochloric acid or sulfuric acid, may be used; organic acids, however, such as formic acid, acetic acid, propionic acid or oxalic acid, are also suitable. The compounds of the Formula I may be obtained in solid form by evaporation of their aqueous solutions under mild conditions. In practice, however, concentrated brightener solutions are preferred to powders since they are easier to handle. Therefore, it is advantageous to dispense with the evaporation. In the following examples, the content of the solutions of the compounds I is mostly referred to the internal salts IV.

The compounds I of the present invention, wherein R and R represent a lower alkyl group or an aralkyl group, are prepared from the internal salts IV, wherein R represents hydrogen, by stirring the salts IV in water with 2 equivalents of sodium hydroxide solution and treating them with at least 4 to about 8 equivalents of an alkylating agent. A (greater) excess of alkylating agent might be used, but is in general of no advantage. As alkylating agents, there may be used the esters of sulfuric acid, such as dimethyl sulfate or diethylsulfate, or the esters of aromatic sulfonic acid, such as the p-toluene-sulfonic acidmethyl ester. Alkyl or aralkyl halides, such as methyl chloride, methyl bromide, ethyl bromide, butyl bromide, benzyl chloride and benzyl bromide may also be used as alkylating agents.

Most of the compounds tested here are already peralkylated at temperatures of up to 50 C. and are dissolved without difliculty. In order to destroy the excess of alkylating agent used it is, however, advantageous to heat the solutions to about 60 C. and keep the solution in the alkaline pH range by adding dropwise sodium hydroxide solution, until no further change of the pH- value occurs. The concentrated solutions of the compound I obtained are used directly for brightening purposes after neutralisation and adjustment to a definite percent content (in general referred to the internal salts IV).

Some compounds of the general Formula I are relatively difficultly soluble in the presence of salts and precipitate from the alkylating solution. Their isolation is carried out in the usual manner by suction-filtering and washing with a solution of sodium chloride. If desired or required, a reprecipitation from water may be effected.

If the preparation of the compounds I of the present invention is started from the internal salts IV wherein R" represents a lower alkyl group, it is sufficient to react these salts in aqueous suspension with at least 2 equivalents of an alkylating agent, for example dimethyl sulfate. The termination of the peralkylation is reached when from the solutions formed of the compounds I no difiicultly soluble internal salts are separated when sodium carbonate is added at a pHwalue of 9.

The preparation of the compounds I of the present invention in the manner last-mentioned is advantageous if highly concentrated salt-free brightening solutions are to be obtained.

Concentrated aqueous solutions of the products I of the present invention may also be obtained by additlon of 2 equivalents of an inorganic and/or an organic acid to the internal salts IV wherein R" represents a lower alkyl u %ll'th6fm0l6, we have found that the compounds of the general Formula I of the present invention are especially suited as optical brighteners for fibrous material, 1n particular for cellulose materials and in an especially advantageous manner for the brightening of paper. For this purpose, the compounds of the present invention which are either in liquid form or dissolved water, are added to the paper pulp in the hollander, optionally before the addition of other auxiliary agents such as, for example, rosin size, aluminium sulfate etc., and by mixing thoroughly the pulp in order to disperse the brightener homogeneously, before forming the sheets in generally known manner on a wire.

These compounds are absorbed quantitatively and are retained in the paper sheet. The 'water flowing off from the wire is free from brightener, i.e. the process can be carried out without loss of brightener and pollution of the waste water.

The compounds of the present invention are clearly superior, in their brightening effect, both in non-sized as in sized and loaded papers, to the anionic brighteners of the type A hitherto used.

The cationic brighteners of the present invention show an equally very good brightening effect when used in coating mixtures for paper.

Furthermore, we have found that the compounds of the general Formula I of the present invention show a particularly good brightening effect when used together with cationic softening agents for fabrics and knit fabrics of cellulose fibers and fibers of regenerated cellulose. These laundry refining agents generally consist of fatty acid ammonium compounds, for example distearyl-dimethyl-ammonium chloride, and are used in laundry in the last rinsing operation in order to obtain soft and downy linen. By this treatment, however, the linen turns yellow to a certain degree. By addition of the compounds of the present invention, this yellowing can be avoided to a large extent.

The usual anionic optical brighteners (of type A) are incompatible with cationic softening agents and are blocked in their action to a large extent.

The products of the present invention show, when applied onto cellulose fibers, very good brightening elfects, especially when used in a strongly acid medium, for example at a pH-value of 1 to 2. Thus, the new cationic brightners may be used sucessfully together with auxiliary agents for the crease-proofing of cellulose fibers, for example with reactance resins, such as dimethylol-ethyleneurea, dimethylol-propylene-urea, dimethylol-monoalkylcarbamate and others. Particularly high degrees of whiteness are obtained if the condensation of the synthetic resins is effected at a pH-value of 1 to 2, as it is usual in moist or wet cross-linking.

The following examples illustrate the present invention but they are not intended to limit it thereto. The parts by weight and parts by volume are in the same ratio as the kilogram to the liter.

EXAMPLE 1 A solution of 36.7 parts by weight of cyanuric acid chloride in 200 parts by volume of acetone was allowed to run into 700 parts by volume of ice water. To this suspension, a solution of 38.1 parts by weight of 4,4'-diamino-stilbene-2,2'-disulfonic acid (96.8% strength) in 400 parts by volume of water and 100 parts by volume of 2 N-sodium hydroxide solution was added dropwise, at a temperature in the range of from 0 to 5 C., and by simultaneous addition of about 90 parts by volume of 2 N- sodium carbonate solution, the pH-value was maintained at 2.5-3.5. When, by indirect diazotation no more diamino-stilbene-disulfonic acid could be detected, the reaction mixture was adjusted to a pH-value of 7 by means of 2 N-sodium carbonate solution.

parts by weight of B-diethyl-amino-ethylamine were added to the suspension of the sodium salt of 4,4'-bis- (2",4"-dichloro s triazinylamino-(6") )-stilbene-2,2'-di sulfonic acid thus prepared, the mixture was heated slowly to 40 C. and this temperature Was maintained, while stirring, for 4 hours. The reaction mixture was then heated to -95 C., while acetone was distilled off, and boiled for 5 hours under reflux. The mixture was then diluted with 1000 parts by volume of water, the reaction product that had precipitated was dissolved at 60-70" C. by addition of about 45 parts by volume of a 33% sodium hydroxide solution, then clarified after addition of 10 parts by weight of charcoal and the clear filtrate was mixed with 520 parts by weight of sodium chloride. The sodium salt of the 4,4'-bis-(2",4"-(,B-diethylamino-ethylamino-striazinylamino-(6") )-stilbene-2,2'-disulfonic acid that had precipitated was filtered off with suction after cooling and washed with a 20% sodium chloride solution.

The sodium salt was dissolved in 1500 parts by volume of water at a temperature of from 50 to 55 C. and the pH-value of the strongly alkaline solution was adjusted to pH 10 by means of concentrated hydrochloric acid. The internal salt (1) (Table 1) that had precipitated crystallized upon further stirring at 15 C. The salt was sepparated by suction-filtration, washed with water until it was free from chlorine ions and dried in vacuo at 60 C. 87 parts by weight of the compound (1) were obtained, corresponding to a yield of 88.5% of the theory.

60 parts by weight of the internal salt 1) were introduced into 150 parts by volume of water and dissolved, while stirring, by adding dropwise about 11 parts by volume of concentrated hydrochloric acid, at a pH of 3-4. The mixture was diluted with water to 300 parts by weight whereby a clear solution of the compound (34) (Table 2) was obtained (20% solution, referred to the internal salt).

49.25 parts by weight of the internal salt (1) were introduced into 100 parts by volume of water and mixed with 50 parts by volume of 2 N-sodium hydroxide solution. To the stirred mixture 25.5 parts by weight of dimethyl sulfate were added dropwise and the temperature was maintained at 3550 C. by cooling. Stirring was continued for 2 hours at room temperature. In order to destroy any present dimethyl sulfate, the solution was subsequently heated to 60 C. while keeping the pH-value at 8 to 9 by dropwise addition to about 6 parts by volume of 2 N-sodium hydroxide solution. By addition of 2 N-sulfuric acid, the pH-value was then readjusted to 7 and the clear solution obtained of the compound (35) (Table 2) was filled up with water to the amount of 246.5 parts by weight (20% solution, referred to the internal salt).

9.85 parts by weight of the internal salt (1) in 50 parts by volume of water were mixed with 20 parts by volume of 2 N-sodium hydroxide solution and 8.8 parts by weight of p-toluene-sulfonic acid-methylester and the mixture was heated to 50 C., while stirring. The mixture Was kept for 4 hours at 50 C., then cooled to room temperature and the clear solution of the compound (36) (Table 2) that had formed was adjusted to a pH-value of 7 by means of concentrated hydrochloric acid. By diluting with water to 98.5 parts by weight, a 10% solution (referred to internal salt) was obtained.

EXAMPLE 2 78 parts by weight of N,N-diethyl-l,3-diaminopropane were added to the suspension of the sodium salt of 4,4- bis-(2",4"-dichloro-s-triazinylamino-(6") )-stilbene 2,2- disulfonic acid, prepared according to Example 1, the whole was heated slowly to 40 C. and maintained, while stirring, for 4 hours at this temperature. The reaction mixture was then heated to 95 C., while acetone was distilling off, and boiled for 5 hours under reflux. The mixture was diluted with 2000 parts by volume of water, the reaction product that had precipitated was dissolved by addition of about 30 parts by volume of a 33% sodium hydroxide solution, clarified after addition of 20 parts by weight of kieselguhr, and the clear filtrate was combined with 230 parts by weight of sodium chloride. The sodium salt of the 4,4'-bis-(2,4"-('y-diethylaminopropylamino) s triazinylamino-(6") )-stilbene-2,2'-disulfonic acid that had precipitated was stirred at room temperature, suction-filtered and washed with a 20% sodium chloride solution. The sodium salt was dissolved in 2000 parts by volume of water at room temperature and to the resulting solution there were added dropwise 50 parts by volume of concentrated hydrochloric acid until the precipitate formed was dissolved. The mixture was clarified by filtration and the filtrate was mixed with 100 parts by weight of sodium carbonate until it showed, with phenol-phthalene, a definitely alkaline reaction. The internal salt (2) (Table 1) which first precipitated in greasy form, was decanted several times with water, until no more chlorine ions could be detected. After drying in vacuo at 60 C., 62 parts by weight of compound (2) in solid form were obtained (60% of the theory).

60 parts by weight of the internal salt 2) were dissolved in 150 parts by volume of water by addition of 7.5 parts by volume of formic acid, at a pH-value of 5. The solution of the compound (37) (Table 2) was filled up with 8 water to the amount of 300 parts by weight (20% solution, referred to the internal salt).

52 parts by weight of the internal salt (2) in 150 parts by volume of water were mixed with parts by volume of 2 N-sodium hydroxide solution and 25.5 parts by weight of dimethyl sulfate. The mixture was stirred for 1 hour at 35 ot 40 C. and subsequently for several hours at room temperature. By addition of 2 parts by volume of 2 N-sodium hydroxide solution, the pH-value was maintained at 8. The solution of compound (38) (Table 2) was filled up with water to 250 parts by weight (20% solution, referred to the internal salt).

EXAMPLE 3 112 parts by weight of N,N-di-n-butyl-1,3-diaminopropane were added to the suspension of the sodium salt of 4,4'-bis-(2",4"-dichloro-s-triazinylamino-(6")) stilbene-2,2-disulfonic acid, prepared according to Example 1, the mixture was heated slowly to 40 C. and this temperature was maintained for 4 hours, while stirring. The reaction mixture was then heated to 95 C., while acetone was distilling off, and boiled for 5 hours under reflux. It was cooled to 15 C., the supernatant was decanted from the reaction product which had precipitated in semi-solid form, and the reaction product was mixed with 2000 parts by volume of water. By addition of about parts by volume of concentrated hydrochloric acid, the reaction product was dissolved, the solution was clarified with 20 parts by weight of kieselguhr, and by addition of 100 pars by weight of sodium carbonate, the internal salt (3) (Table 1) was precipitated and suction-filtered. After washing to remove the chlorine ions and drying at 60 C. in vacuo, 119 parts by weight (94% of the theory) of compound (3) were obtained.

60 parts by weight of the internal salt (3) were dissolved in 150 parts by volume of water by addition of about 6 parts by volume of formic acid at a pH-value of 5-6. The solution of compound (39) (Table 2) was filled up with water to 300 parts by weight (20% solution, referred to the internal salt).

EXAMPLE 4 95 parts by weight of 1-diethylamino-4-amino-pentane were added to the suspension of the sodium salt of 4,4- bis-(2",4"-dichloro-s-triazinylamino-(6")) stilbene 2, 2'-disulfonic acid, prepared according to Example 1, the mixture was heated slowly to 40 C. and maintained at this temperature for 4 hours, while stirring. The reaction mixture was then heated to 95 C., while acetone was distilling off, and boiled for 5 hours under reflux. Then it was cooled to 20 C., the supernatant was decanted from the reaction product which had precipitated in resinous form, and the reaction product was dissolved by addition of 500 parts by volume of 2 N-hydrochloric acid and 1500 parts by volume of water. After having been stirred, the solution was clarified with 20 parts by weight of kieselguhr and the internal salt (4) (Table 1) was precipitated by addition of parts by weight of sodium carbonate (until definite alkaline reaction with phenolphthaleine). The compound which crystallized only difliculty was mixed several times with water in order to remove the chlorine ions, and dried at 60 C. in vacuo. 101 parts by weight of compound (4) corresponding to 88% of the theory, were obtained.

60 parts by weight of the internal salt (4) were dissolved in parts by volume of water by addition of 4.5 parts by volume of formic acid at a pH of 5-6. The solution of compound (4) (Table 2) was filled up with water to 300 palrtt)s by weight (20% solution, referred to the internal sa EXAMPLE 5 A solution of 27.2 parts by weight of 3-amino-dimethylaniline in 50 parts by volume of acetone were added to the suspension of the sodium salt of 4,4'-bis-(2",4"-dichloro-s-triazinylamino-(6") )-stilbene-2,2'-disulfonic acid,

prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept for 4 hours at this temperature. By adding dropwise 66 parts by volume of 2 N-sodium carbonate solution, the pH-value was maintained at 7. Then 46.5 parts by weight of p-diethylamino-ethylamine were added, the reaction mixture was heated to 95 C., while acetone was distilling olf, and boiled for 5 hours under reflux. It was then cooled to room temperature, the supernatant was decanted from the reaction product which had precipitated in resinous form, and the reaction product was dissolved by addition of 500 parts by volume of 2 N-hydrochloric acid and 1000 parts by volume of water. After stirring, the solution was clarified with parts by weight of kieselguhr, and by adding 100 parts by weight of sodium carbonate at pH 9-10 the internal salt (5) (Table 1) was precipitated. The crystalline product was suctionfiltered, washed until itw as free from chlorine ions and dried at 60 C. in vacuo. 98 parts by weight of compound (5) were obtained, corresponding to 96% of the theory.

30.7 parts by weight of the internal salt (5) in 100 parts by volume of water were mixed with 30 parts by volume of 2 N-sodium hydroxide solution and 22.7 parts by weight of dimethyl sulfate and the whole was stirred for 7 hours at room temperature. By adding dropwise 2 N-sodium hydroxide solution, the pH-value was maintained at 8 to 9. 34 parts by volume of 2 N-sodium hydroxide solution were necessary therefor. The supernatant was decanted from the reaction product which had precipitated in resinous form, and the reaction product was stirred with a 10% sodium chloride solution until crystallization occurred. The mixture was suction-filtered, washed with a 10% sodium chloride solution and dried at 60 C. in vacuo. 33 parts by weight of compound (41) (Table 2) were obtained. With regard to a content of 3.5% of sodium chloride, the yield corresponds to 92% of the theory.

EXAMPLE 6 A solution of 27.2 parts by weight of 3-amino-dimethylaniline in 50 parts by 'volume of acetone were added to the suspension of the sodium salt of 4,4'-bis-(2",4"- dichloro-s-triazinylamino (6")) stilbene-2,2-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept for 4 hours at this temperature. By adding dropwise about 100 parts by volume of 2 N-sodium carbonate solution, the pH-value was constantly maintained at 7. Then 46.4 parts by weight of fl-diethylaminoethylamine were added, the reaction mixture was heated to 75-80" C. while acetone was distilling off, and kept at this temperature for 1 hour. The reaction product, which crystallized during cooling, was suction-filtered, crushed to small pieces and washed with water on a suction filter until it was free from chlorine ions. The material obtained from the suction filter was introduced into 2000 parts by volume of water, 100 parts by volume of 2 N-sodium hydroxide solution were added and, after short stirring, a solution was obtained from which small impurities were removed by suction-filtering. 25.2 parts by weight of dimethyl sulfate were added dropwise in about 5 minutes to the clarified solution, the internal salt (7) (Table 1) precipitating thereupon. The suspension obtained was heated to 60 C. in order to convert the compound (7 into a coarse grained crystalline form, the suspension was kept for minutes at this temperature, suction-filtered and the material obtained from the suction filter was washed with 3000 parts by volume of water. After drying at 60 C. in vacuo, 97 parts by weight of compound (7) were obtained (92% of the theory).

150 parts by weight of compound (7) were introduced into 500 parts by volume of water, combined with 35.8 parts by weight of dimethyl sulfate and stirred for 3 hours at room temperature. The solution obtained was then heated for minutes to 70-80 C. and, after having been cooled, it was filled up with water to 925 parts 10 by weight. A 20% solution of compound (44) (Table 2) was obtained.

EXAMPLE 7 A solution of 32.8 parts by weight of 4-aminodiethylaniline in 50 parts by volume of acetone was added to the suspension of the sodium salt of 4,4-bis-(2",4"-dichlorotriazinylamino-(6)) stilbene-2,2'-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperature, then heated to 40 C. and kept at this temperature for 2 hours. By adding dropwise 35 parts by volume of 2 N-sodium carbonate, the pH was constantly maintained at 7. Then, 46.4 parts by weight of fi-diethylamino-ethylamine were added, the reaction mixture was heated to C. while acetone was distilled off, and boiled for 5 hours under reflux. After cooling and continuing the stirring for some time, the crystalline reaction product was suction-filtered and washed twice with water. The material obtained from the suction filter was introduced into 1000 parts by volume of water, dissolved by addition of 40 parts by volume of concentrated hydrochloric acid, and the solution obtained was clarified, after stirring, with 5 parts by weight of kieselguhr. The filtrate was mixed with parts by weight of sodium carbonate, stirring was continued for 3 hours at room temperature, the crystalline internal salt (6) (Table l) was suction-filtered, washed until it was free from chlorine ions and dried at 60 C. in vacuo. 105.5 parts by weight were obtained, corresponding to 98% of the theory.

32.4 parts by weight of the internal salt (6) were mixed in 100 parts by volume of water, with 30 parts by volume of 2 N-sodium hydroxide solution and 22.7 parts by volume of dimethyl sulfate and stirring was continued for 7 hours at room temperature. By adding dropwise 2 N-sodium hydroxide solution, the pH-value was maintained constantly at 8-9. 37.5 parts by volume of 2 N- sodium hydroxide solution were necessary therefor. The reaction product which had precipitated in crystalline from was suction-filtered and dissolved in 500 parts by volume of water at 70 C. This solution was clarified hot by addition of 5 parts by weight of charcoal and 5 parts by weight of kieselguhr, and mixed with 70 parts by weight of sodium chloride. The mixture was allowed to cool, while stirring, washed with a 10% sodium chloride solution and dried at 60 C. in vacuo. 29' parts by weight of compound (42) (Table 2) were obtained. With regard to the content of 5.5% of sodium chloride, the yield corresponds to 75.5% of the theory.

EXAMPLE 8 A solution of 32.8 parts by weight of 4-amino-diethylaniline in 50 parts by volume of acetone was added to the suspension of the sodium salt of 4,4'-bis-(2",4"-dichloro-s-triazinylamino (6)) stilbene 2,2-disulfonic acid, prepared according to Example 1. The mixture was stirred for 2 hours at room temperautre, then heated to 40 C. and kept for 2 hours at this temperature. By dropwise adding about 50 parts by volume of 2 N-sodium carbonate solution, the pH-value was constantly maintained at 7. Then 46.4 parts by Weight of B-diethylamino-ethyl amine were added, the reaction mixture was heated to 7580 C. while acetone was distilling off, and maintained at this temperature for 1 hour. The reaction product which crystallized upon cooling, was suction-filtered, crushed to small pieces and washed on a suction filter until it was free from chlorine ions. The material obtained from the suction filter was introduced into 500 parts by volume of ethanol and 1500 parts by volume of water, 100 parts by volume of 2 N-sodiurn hydroxide solution were added, and, after short stirring, a clear solution was obtained. 32.2 parts by weight of dimethyl sulfate were added dropwise to this solution in about 5 minutes, whereupon the internal salt (8) (Table 1) precipitated at first in greasy form. When stirred at room temperature, the salt became solid. It could be suction-filtered and washed with water after having been crushed to small pieces. After 1 1 drying at 60 C. in vacuo, 103 parts by weight of compound (8) were obtained (93% of the theory).

110.8 parts by weight of compound (8) were introduced into 400 parts by volume of water, combined with 25.2 parts by weight of dimethyl sulfate and stirred for 3 hours at room temperature. The solution obtained was then heated for 30 minutes to 7080 C. and after cooling, it was filled up with water to 680 parts by weight. A 20% solution of compound (45) (Table 2) was obtained.

EXAMPLE 9 A solution of 27.2 parts by weight of 4-amino-dimethyl-aniline in 50 parts by volume of acetone was added to the suspension of the sodium salt of 4,4-bis-(2",4"-

EXAMPLE 10 'By operating according to the method described in 'Example 9, using 27 parts by Weight of 4-amino-dimethylaniline and 52 parts by weight of N,N-diethyl-'1,3-diaminopropane, 91 parts by weight of compound (10) (Table 1) were obtained, corresponding to 84.5% of the theory.

117 parts by weight of the moist compound (10) (46.2%, strength corresponding to 54.1 parts by weight of a 100% compound) were mixed by stirring for 2 hours at room temperature in 125 parts by volume of water,

diqhloro s triazinylfiminoiw"))'stilbene'zzfdisulfonic 1D with 12.6 parts by weight of dimethyl sulfate, until a i Prepared accordmg to Example The mlxture was clear solution was obtained. This solution was heated to Stll;1'd for 2 hours at room temperature, then heated to for 30 minutes and after cooling it was filled 3023; 5 3 g} 1 32533 22 ggiz g 5' $5 5 a: 3 up with water to 332 parts by weight. A solution 1 value was maintained constantly at 7. The 46.6 parts by 20 of compound (47) (Table 2) was obtamed' weight of S-diethylamino-ethylamine were added and the EXAMPLE :11 reaction mixture was heated to 7080 C., while stirring 134 parts by Weight of the moist compound (11) g9 2 .2 2 2 g if fz g: (Table 1) (17.75% strength, corresponding to 23:8 parts i i nfi ltb red aft f' bg ol i g i o r oo in femp eratl i i'e a ild 25 by weight a 100% compound) were stirred with washed The moist material obtained from the suction Parts by Welght 9 benzyl ch10ride.for 24 hours at room filt 1 d 2000 arts b Volume of water and temperature. A highly viscous solution of compound (49) 5 er was 1850 we 1 p y (Table 2) was obtained, containing, after filling up with 00 parts by volume of ethanol, with addition of 100 Water to 150 parts b Wei ht 207 of this bri htem parts by volume of 2 N-sodium hydroxide solution, and in a em y g o g the solution was clarified at 50 C. To the filtrate obg g EXAMPLE tained, 25.2 parts by weight of dimethyl sulfate were added dropwise and the methylation product that had 260 parts by weight of the moist compound (12) precipitated was suction-filtered. The methylation product (Table 66% Streng orresponding to 43.2 parts was then washed with 2000 parts by volume of water and r y Weight of 100% Compound), WW3 Stirred for 24 hours dried at C. in vacuo. 92 parts by weight of com- 30 at room temperature, after addition of 200 parts by volpound (9) (Table 1) were obtained, corresponding to 111116 of Water, With 11 Parts y Weight of belllyl ch10- 87.5% of the theory. ride. After filling up with water to 533 parts by Weight,

199 parts by weight of compound (9) (31.7% strength, a 10% viscous solution of compound (51) (Table 2) was corresponding to 63 parts by weight of a com- 40 btained. pound) were mixed by stirring for 2 hours at room term The following Table 1 indicates the internal salts of perature, in parts by volume of water, with 15.15 the Formula IV of the present invention, and Table 2 parts by weight of dimethyl sulfate until a clear solution lists the cation-active compounds of the 'Formula I of the had formed. This solution was heated to 70-80 C. for present invention.

TABLE 1 Analysis, percent Calculated Found Number R R N S Org. C N S Org. Cl

1 NHCH:CHzN(C2H5)z H 22.8 6.5 22.8 6.6 0.3 NH- CH2 Olin-1 3} CaHr) 2 2 NHCH2CH1CHzN(CzH5)z H 21.5 6.15 20.9 6.3 0.3

NH-CHzCHnCHa-(IltIfCzHa):

3 NHCHzCHzCHz-NULHo): H 17.7 5. 06 17.5 4.5 0.3

NHCH2CH3CHz-(NL(C4H9)1 4 NH-CH-CHgCHzCHzN(CzH )z CH3 H 19.4 5.55 19.2 5.6 (0.3

CH NH-CHCH:CH1CH2L(C:H&)2

5 NH 1X1 21.9 6.25 21.4 5.7 0.5 NHCH2CH2-1;(C2 s)z s):

0 Same as above-.- 20.7 5.9 20.5 5.6 (0.3

N H-Q-N (C211 TABLE 1--Cont1nued Analysis, percent Calculated Found Number R R N S Org. 01 N S Org. C

NHCH2CHz I; (CzH5)1 s):

8-.'. Same as above 20.25 5.8 19.8 5.6 0.3

NH N(C2H NH N(CH3)2 10..-:753'32'; Sameasabove..--nz;--;;.';:.:::;.;:;;: $11 20. 75 5.9 20.7 6.2 0.5

NH-CH2CH2-CH2I (C2H5)2 11 Sameas above (iJHa 18.8 5.4 18.8 5.7 0.3 NHCH2C 2C 2g (C4 v)2 12 N(CH3)2 (IJHa 20.7 5.95 20.8 5.8 0.3

Q NHCHzCHgCH2N C2H5h NH- 13 Sameasabove- (3H3 18.8 5.4 18.6 5.3 0.3 NHCH2CHZCH2 C4HQ2 NHcmomcmN o NHomomomJN 2) 15 N(CH3)2 H 20.75 5.93 20.9 5.9 0.3

I NHCHgCHzCHz-N 2) NH 16 Same as above.. CH5 20.25 5.8 20.2 5.5 0.3

NHCHzCHzCHz-N O NHCH2CH2CH2N H I NHcHzcH cHzTgl H 18 N(CHs)z Sameasabove 20.8 5.95 21.0 5.6 0.3

19 Sameasabuve CH3 20.3 5.8 20.0 6.1 0.3

NHCHgCHgCHz-N H 2o NHCH2(|)HCH2N(C2H5)2 I I 20.3 5.8 20.0 6.2 0.3

OH NHCH2?HCHzRI)(CzH5)2 21 N(CH5)2 Same as above 20.65 5.9 20.4 5.8 0.4

22 Same as above ('THa 20.15 5.75 19.6 6.1 0.3 NHCHflllHcHza fcz flz 23 NHCHaCHzCH2IIICaHu 20.2 5.8 19.8 5.9 0.3

CH3 NHCHgCHgCHz)(CzH5)g 24 Same as above CH; 19.75 5.6 19.1 6.2 0.3

NncflgcHgcHzNghfiah 25 N(CH3)2 (3 3 20.0 5.7 19.9 5.5 0.3 NHCHzCH2CHgNHCuH5 NH- 26 Same as above (C O: 19.5 5.6 19.3 5.4 0.3

TABLE 1-Continued Analysis, percent Calculated Found Number R R N B Org. 01 N B Org. Cl

27 N(CH: .)2 III 20. 75 6.9 20. 5 6. 1 0.3

NHCH2CH2C 2N(C1 5)z NII- 28 Sameasabove ?H; 20.2 5 8 20 6.1 0 3 NHCHzCHzCHzg)(CzH )g 29 II T(CH)I ZII 20.75 5 9 6 5.8 0 3 NHCH CH CH C H NH-Q-QH, 2 3f 30 Same as above (13H; 20.2 5.8 20.1 6.0 0.3

NHCHzCHzC 2a 2 O1 31 .-d0 I? 20.0 5.7 19.3 5.3 0.3

NH- CH;

NHCHzC zC 2 (C2 5)z NH- N(GH=)1 33 Same as above (3H, 19.5 5.6 6.2 19.5 5.6 6.2

NflCHgCHaCHzgmCz bh TABLE 2 R 2+ N K =CH- NH- N 21:-

Number R X- 34 I? III Cl- NH-CHzCHz-(1)(C:H5)z NHCHzCHz-(I;1)'(C:H5)z

35 (EH; 111 CHaOSOg NHCHzCHzH)(CzH5)2 NHCHzCH:%j;(CgH5)1 36 Same as above Same as above CHzCoH4SOF NHCHzCHzCHg-EKCJL), NHCHzCHgCHz-(I$(C:H5)z

38 CH3 CH3 CHBOSOI HNCH1CHzCHz-H)(CH5)2 NHCHZOHZCHPPJCZHE)! 39 III 1'1 H000 NHCH:CH3CH)%)(C4H9)1 NHCHzCH2C r-g(C4 0)2 40 1?: (EH; 1'1 Same.

NHCH-CHgCHzCHza;(CzH5)2 NHCHCH;CHzCHr-)(C:H3)z

| NH- NH- C H1O C2115) I I 42... Same as above (EH; Same.

NH@ z s):

3 -.:::'..r:::::::::: CH; CH; 0113050;-

NHCHICHICHi-EffClHD) 19 EXAMPLE 13 100 parts of dry, bleached soft wood sulfite pulp ground in a 4% aqueous suspension, in a hollander, to a beating degree of 40 SR. Then, 0.25 percent by weight of compound (37), referred to absolutely dry fibers, which had been previously dissolved in water, were added and the suspension was stirred thoroughly for about minutes in order to disperse the brightener homogeneously. Finally the suspension was diluted with water in known manner to 0.5-1.0% by weight of pulp consistency, and run on a paper wire. The paper sheet that formed passed through the usual drying devices (wet pressing, drying cylinder). The water running off from the wire was free from brightener, the brightener remaining quantitatively in the paper. A comparison with a paper prepared without brightener showed that, by the indicated addition of the compound (37), the whiteness degree was greatly increased.

EXAMPLE 14 100 parts of dry bleached soft wood sulfite pulp were adjusted, in a 4% aqueous suspension, in a hollander, to a beating degree of 40 SR. This suspension was combined with 15%, referred to the fiber weight, of china clay, mixed thoroughly, and then combined with 0.3%, referred to the fiber weight, of compound (41) which had been previously dissolved in water in a dilution of 1:100, and again thoroughly mixed. After further addition of 3% by weight, referred to the fiber weight, of resin size, the suspension was adjusted to a pH of 4.5 by means of aluminum sulfate and mixed until it was homogeneous. After subsequent dilution to 0.5-1.0% by weight of solid material the sheets were formed in usual manner on a wire. Finally, the paper was dried as described in Example 7. Herein too, the brightener remained quantitatively in the paper and the water from the wire was free from brightener. Compared to a non-brightened paper the degree of whiteness was greatly increased by addition of compound (41).

EXAMPLE 15 There was prepared in known manner a paper coating mass (casein coating mass) having the following composition:

After having mixed the components (solids in dispersed form) in the indicated order, 10 g. of a solution of compound (37) were added per liter of coating mass and the coating mixture was adjusted with water, at 20 C., to a viscosity of about 1000 centipoises (Brookfield Viscosime-ter, 20 r.p.m.).

The coating mass so prepared was applied by means of a coating blade on wood-free paper having a weight of 90 g./m. The dry coating amounted to 20 g./m. of paper. The paper was then dried and calendered in the usual manner.

The paper coated and calendered in this manner showed a considerably better whiteness as a paper coated without addition of the compound (37).

20 EXAMPLE 16 Laundry refining agents were prepared using the following components:

(B) Same as (A) but with addition of 0.1 part active substance) of the anion-active optical brightener having the constitution (C) Same as (A) but with addition of 0.1 part of compound (41) (100% active substance).

Bleached white cotton fabrics were washed in the usual manner with a commercial brightener-containing detergent, then rinsed warm and cold, the last rinsing bath containing 4% of softening agent referred to the weight of the dry fabrics.

The after-treatment with agent (A) had produced a distinct yellowing which could not be removed even by application of an anion-active brightener according to Example (B). Only when applying the compounds of the present invention Example (C), the yellowing could be largely supressed.

In order to support the visual evaluation the remission values of the test fabrics were measured in a Zeiss Elrepho apparatus (at 460 mm, remission values R, referred to MgO: 1000).

Result: R Fabric non-treated 974 Fabric washed 1066 Fabric washed and aftertreated with agent A 1012 Fabric washed and aftertreated with agent B 1024 Fabric washed and aftertreated with agent C 1042 EXAMPLE 17 Bleached cotton fabric was impregnated with a solution containing 1 2 g./l. of compound (37) (Table 2), and g./l. of dimethylol-methoxyethyl-carbamate Bleached cotton was impregnated with a solution containing 3 g./l. of the compound (37) (Table 2) 200 g./l. of dimethylol-4,S-dihydroxyethylene-urea, and 100 ml./l. of concentrated hydrochloric acid.

The fabric was squeezed between rollers with a squeezing elfect of 70%. The fabric was rolled up, wrapped in a foil and allowed to stand for 20 hours at room temperature and then rinsed in water at 40 C., with addition of sodium carbonate, until it showed neutral reaction. The fabric treated in this manner showed an excellent degree of whiteness.

We claim:

1. A compound of the formula wherein A and A each is an alkylene of 2 to carbon atoms, hydroxy-alkylene of 2 to 5 carbon atoms, 1,4-dimethylene-cyclohexane, cyclohexylene, 1,4-dimethylenebenzene, 4-benzylene, 4-phenethylene, phenylene, toluylene, chlorophenylene or brornophenylene, R and R each is hydrogen or lower alkyl, R R R and R each is lower alkyl, benzyl, phenyl or cycloalkyl of 5 to 8 carbon atoms, or R and R and/or R and R together with the nitrogen atom are a six-member saturated heterocyclic ring, R; and R each is hydrogen, lower alkyl or benzyl, and X is a colorless anion of a strong mineral acid, formic acid, acetic acid, propionic acid or oxalic acid, a mono-methyl or mono-ethyl ester of sulfuric acid, or a mono-methyl or mono-ethyl ester of an aromatic sulfonic acid.

2. A compound according to claim 1 wherein A and A each is an alkylene of 2 to 5 carbon atoms, phenylene, toluylene or chlorophenylene, R and R each is hydrogen, R R R and R each is lower alkyl or phenyl, or R and R and/ or R and R together with the nitrogen atom is morpholino or piperidino, R and R each is hydrogen, methyl or 'benzyl, and X is chloride, methosulfate, toluene sulfonate or formate.

3. The compound of the formula NH (CH2) NH( C2115)? ZHCOn' 4. The compound of the formula 5. The compound of the formula 6. The compound of the formula N(CH3) 3 2 7. The compound of the formula 8. The compound of the formula 2HCOF 9. The compound of the formula 10. The compound of the formula (References on following page) 24 References Cited FOREIGN PATENTS UNITED STATES TS 528,445 7/1956 Canada 260240 B 1,479,540 3/1967 France 260--240 B 4/1965 Hoelzle et a1. 260249.6 X

4 19 5 Konishi et 1 2 0 24 E 5 JOHN D. RANDOLPH, Primary Examiner 101/ 1966 Andrew et a1 260240 B US. Cl. X.R.

2/1968 Gold et a1. 260-240 B 8-1162; 106148, 176; 117-335 T; 162162; 252- 152, 301.2 W; 260?A0.1 

